Process for forming dye images

ABSTRACT

A PROCESS FOR FORMING DYE IMAGES WHEREBY A PHOTOGRAPHIC SILVER HALIDE EMULSION LAYER IS SUBJECTED TO RADIATION SO AS TO CREATE CENTERS FOR DEVELOPING WITHIN THE SILVER HALIDE GRAINS, SUBJECTING THE EXPOSED SILVER HALIDE TO A COMPOUND RESORCINOL, M-AMINOPHENOL, NAPHTHOL OR DERIVATIVES THEREOF AND TO A POLYMERIZABLE VINYL COMPOUND CAPABLE OF BEING ELECTRICALLY CHARGED BY IONIZATION OR BY THE ADDITION OF A HYDROGEN ION, POLYMERIZING THE VINYL COMPOUND WITH SAID ACTIVATED SILVER HALIDE GRAINS AND DYEING THE RESULTING IONIZABLE POLYMER WITH A DYE HAVING AN ELECTRIC CHARGE OPPOSITE TO THE POLYMER.

Sept. 4, 1973 YOSHIHIDE HAYAKAWA ET AL PROCESS FOR FORMING DYE IMAGES Original Filed April 8, 1968 2.0 INVENTOR Yoshihide Huyokowo III Mosoto Sc'rurmuro BY 4 ww, z ny 4 ATTORNEYS United States Patent Oflice Patented Sept. 4, 1973 Claims priority, application Japan, Apr. 8, 1967, 42/ 002 Int. Cl. G03c 5/26, 1/68 US. Cl. 96-48 R 31 Claims ABSTRACT OF THE DISCLOSURE A process for forming dye images whereby a photographic silver halide emulsion layer is subjected to radiation so as to create centers for developing within the silver halide grains, subjecting the exposed silver halide to a compound resorcinol, m-aminophenol, naphthol or derivatives thereof and to a polymerizable vinyl compound capable of being electrically charged by ionization or by the addition of a hydrogen ion, polymerizing the vinyl compound with said activated silver halide grains and dyeing the resulting ionizable polymer with a dye having an electric charge opposite to the polymer.

This is a continuation of application Ser. No. 719,592, filed Apr. 8, 1968, and now abandoned.

BACKGROUND OF THE INVENTION This invention relates to a process for forming dye images, and more particularly to a process for forming dye images by reaction induced by a reaction between a silver halide photographic emulsion and a reducing agent.

There have been known various methods of forming dye images by making use of a silver halide photographic emulsion. It has been proposed to develop latent images formed in silver halide photographic emulsion with pphenylenediamine developing agent in the presence of couplers to form dye images composed of the oxidation products of the developing agent and a coupler.

In this case, there are such difiiculties that free selection of the dyestuffs for the colored images is impossible and an excellent hue and fastness cannot be obtained, since the dyestuffs for the colored images are restricted to those which can be formed by the reaction between the oxidation product of the developing agent and the couplers.

It has been further proposed to utilize a tanning development process, in which gelatin relief images corresponding to latent images formed in gelatino silver halide emulsion layer are obtained by developing with tanning developers such as pyrogallol in the absence of sulfite to harden the emulsion layer by the oxidation products of the developer and removing the unhardened portions by washing with water.

Dye images can be formed by subjecting the gelatin relief images to absorb a mordant dye and transferring the mordant dye to a mordant paper. Although the dyes having an excellent hue and fastness can be used in this procedure, the soft gelatin relief images tend to be scratched and inconvenient to the use.

We have shown in Japanese patent application Nos. 36,388/66, 6,213/67, 6,214/67 and 11,109/67 that when a latent image formed by exposing a silver halide photographic emulsion layer imagewise to an electromagnetic wave or particle rays is developed with resorcinol, maminophenol, or naphthol derivative in the presence of a vinyl or vinylidene compound, the image of the polymer corresponding to the exposed parts are obtained as the result of the polymerization induced by the reaction intermediates produced thereby.

BRIEF DESCRIPTION OF THE DRAWINGS FIGS. 1 and 2 are characteristic curves showing the relationship between density and exposure of films provided by the present invention.

SUMMARY OF THE INVENTION An object of the present invention is to provide a process for forming dye images in the areas exposed imagewise to electromagnetic waves or particle rays by utilizing a dye capable of having an electric charge by electrolytic dissociation without utilizing soft gelatin relief images. Another object of the present invention is to provide a process for reproducing dye images by transferring the dye images.

We have now discovered that where a vinyl compound of the type mentioned above has a group capable of having an electric charge, due to electrolytic dissociation or the addition of a hydrogen ion, a polymer capable of having an electric charge, due to the electrolytic dissociation or the addition of hydrogen ions, is obtained and the image composed of the polymer can be dyed selectively with a dye having an electric charge opposite to the polymer. Moreover, we discovered that dye images thus formed can be transferred to another support by various processes.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention consist in subjecting a photographic silver halide emulsion layer which has received selective exposure to radiation such as electromagnetic waves or particle rays, such that centers for developing are created within at least a portion of the silver halide grains, in either the areas that have received or have not received said exposure, to the action of at least one compound represented by resorcinol, its derivatives, m-aminophenol, its derivatives or naphthol derivatives having two hydroxy groups, or one hydroxy group and one amino group in 1,6-positions, 1,8-positions, 2,5-positions or 2,7- positions on the naphthalene ring in the presence of a polymerizable vinyl compound or compounds capable of having an electric charge by ionization or addition of a hydrogen ion, polymerizing said vinyl compound or compounds in the area in which development centers exist in many silver halide grains, and dyeing the resulting ionizable polymer selectively with a dye having an electric charge opposite to the polymer.

In the practice of the present invention there may be used ordinary silver halide emulsions that form centers of development in the areas irradiated by electromagnetic waves or particle rays and yield negative images, and there may also be used so-called direct positive emulsions that form centers of development in the unexposed silver halide particles more than in the exposed silver halide particles.

In the present invention, as a silver halide photographic emulsion that gives a negative image, an emulsion which is suitable for ordinary developing processes can conveniently be used. Thus, silver chloride, silver bromide, silver chlorobromide, silver iodobromide and silver chloro-iodobromide photographic emulsions can be used. Chemical sensitization and/or optical sensitization which are applicable to ordinary photographic emulsions can be applied to the silver halide emulsions for the present invention. Thus sulfur sensitization and noble metal sensitization are applicable for the chemical sensitization (see for example, P. Glafkides, Chemie Photographique, 2d Edition, Photocinema Paul Montel, Paris, 1957, pp. 247-301). As for optical sensitization, optical sensitizers for ordinary photographic emulsions, such as cyanine dyes and merocyanine dyes, can be used conveniently (see for example, Kikuchi et al., Kagaku Shashin Benran (Handbook of Scientific Photography), vol. II, pp. 15-24, Maruzen Co., Tokyo, 1959). The emulsion to be used in the present invention may also contain stabilizers as employed in the conventional photographic techniques.

The direct positive silver halide emulsion which can be employed in the present invention may be prepared by applying solarization, Herschel effect, Clayden effect or Sabatier effect. On these effects full explanations are given in Chapters 6 and 7, by C. E. K. Mees, of The Theory of the Photographic Process, the second edition, published by Macmillan & Co., 1954. To prepare direct positive silver halide photographic emulsions applying solarizatlon, silver halide emulsion susceptible to solarization is prepared and then, subjected to uniform exposure to light or to the action of a chemical reagent to render it developable without imagewise exposure. The methods of preparation of such emulsions are disclosed in British Patent Nos. 443,245 and 462,730.

The Hershel effect is produced by exposing to light of longer wavelength a photographic emulsion which has been rendered developable by a uniform exposure to light of shorter Wavelength or a uniform action of a chemical reagent. In this case it is preferable to use a silver halide emulsion containing silver chloride for the most part and a desensitizer, such as, phenosafranine or pynakryptol yellow, may be added to the emulsion to enhance the elfect. The method of preparation of direct positive emulsions applying the Hershel effect is disclosed in British Pat. No. 667,206 and US. Pat. No. 2,857,273.

In order to obtain a positive image directly by using the Clayden effect, it is necessary to subject an emulsion to over-all exposure to light of a relatively low intensity, after imaging exposure to light of a high intensity for a short period of time. In this Way, the areas of the emulsion which have not been exposed to irradiation by the high intensity light become developable, after the over-all exposure.

The Sabatier effect is produced by exposing to a uniform action of light or a chemical reagent, in a state of immersion in a developing solution, a silver halide photographic emulsion layer that has received imaging exposure to light. This gives rise to development capability in the area that has not been exposed to the imaging exposure. The Clayden effect and Sabatier effect are easily and practically obtained in silver halide emulsions that have a tendency to yield centers of development, by the first exposure, in the inner portion rather than in the surface portion of grains of silver halide. The method of preparing such emulsions that have a tendency to yield internal centers of development is disclosed in US. Pat. Nos. 2,592,250 and 2,497,876, British Pat. No. 1,011,062 and German Pat. No. 1,207,791.

The photographic emulsions mentioned above consists of dispersion systems in which particles of silver halide are dispersed in a solution of a high polymer. As the high polymer for this purpose gelatin is widely employed. However, synthetic high polymers, such as, polyvinyl alcohol, polyvinyl pyrrolidone and polyacrylamide or naturally occurring high polymers, such as, carboxymethyl cellulose, oxyethyl cellulose and dextran may also be employed, either alone or in mixtures with gelatin (refer to F. Evva: Zeitschrift fur Wissenschaftliche Photographic, Photophysik und Photochemie, Vol. 52, pages 1-24, 1957).

The compound to be employed in the present invention includes, for example, resorcinol, m-aminophenol and their derivatives as follows:

Bcscrclncl ltcsorcluol-mouoacctlc acid ester H (I) H? (llHz Resorclnol monoethylether Z-methyl-resorcinol H O H? 3- Q- (IJH3 C2H5 fi-methyl-resorcinol 4-ethyl-resorclno1 H0 H? Q I 00 1: C O OH 4-hcxyl-resorcln0l 3,5-dlhydroxy bcnzolc acid HI) (3 0 OH 01? If 02 2,6 dlhydroxy bcnzolc acid 2-nitroresorclnol H 0 (RH H0 OH Phlorogluclnol 1,3-naphthalene-d1ol H O OH:

NH N 2 m-Amlnophenol m-(Dlmethylamino) phenol HO HO O H: N NH(CH2)aSOzH C C H:

4-hydroxy-N,N-dlmethy1-o- 3- (m-hydroxyanlllno)-1-propanetoluidlne sullonic acid HO H? m-Hydroxyphenylgluclne m-(Benzylamino)phonol H0 H0 @uvncrnomon Q-nucmcmot m-(B-Hydroxyethylamlno) m-(fl-Chloroethylamlno)phenol phenol OH OH I @oolm @-oco@ resorcinolmonoethylresorcinolrnonobutylresorcinolmonoether ether benzoate 0 H OH OH CIHIO H OH OH OH I I Cs 1- CsHu-t o-Ilydroxyeth yl-= 4-n-pr0pyllcs0rciu0l 4-t-octylresorclnol rcsorciuol OH OH 1,8-dihydroxynaphthalcne-3,5-

disuiionic acid tiJH OH OH OH HO- OH H0 8 S a HOaS- S 0:11

1,8-dihydroXynaphthalcne-Ii,6-

disulfonic acid 2,7-dihydroxynaphtl1alene-3,6-

disulfonic acid HO HO l-amino-G-naphthol 3-(6-hydroxy-l-naphthylamino) propane-l-sulfonlc acid OH NH; OH NHCOCHa 1-amino-8-naphthol 2-amino-5-naphthol 2-amlno-7-naphthol N-acctyl-l-amino-S-naphthol O H NH2 WQONH.

l-arnino-S-naphthol- 2,4-disulionic acld The process for synthesis of such phenolic and naphtholic compounds is well known in the art, and the compounds are commercially available.

The vinyl compounds to be employed in the present invention include normally liquid and solid compounds capable of addition-polymerizing and having an electric charge by ionization or addition of hydrogen cation.

As the addition polymerizable vinyl compounds capable of having an electric charge by ionization or addition of hydrogen cation, there may be employed, in the present invention, a carboxylic acid having a vinyl group such as acrylic acid, methacrylic acid or maleic acid, an ammonium salt of carboxylic acid having a vinyl group such as ammonium acrylate, a metallic salt of carboxylic acid having a vinyl group such as sodium acrylate, potassium acrylate, calcium acrylate, magnesium acrylate, zinc acrylate, cadmium acrylate, sodium methacrylate, calcium methacrylate, magnesium methacrylate, zinc methacrylate, cadmium methacrylate, sodium itaconic acid or sodium maleic acid, a sulfonic acid having a vinyl group such as vinyl sulfonate or p-vinyl-benzene sulfonate, an ammonium salt of sulfonic acid having a vinyl group such as ammonium vinyl sulfonate, a metallic salt of sulfonic acid having a vinyl group such as sodium vinyl sulfonate, potassium vinyl sulfonate or potassium p-vinyl-benzene sulfonate, which are polymerized to have a negative electric charge, a vinyl compound having a basic nitrogen atom such as 2-vinyl-pyridine,

4-vinyl pyridine, 5-vinyl-2-methyl-pyridine, N,N-dimethylaminoethylacrylate, N,N-dimethyl-aminoethylmethacrylate, N,N-diethylaminoethylacrylate, N,N-diethylaminoethyl-methacrylate,

and a quaternary salt having a vinyl group produced by reacting a compound having a vinyl group and a basic nitrogen atom with methyl chloride, ethyl bromide, dimethyl sulfate, diethyl sulfate or methyl p-toluene-sulfonate which are polymerized to have a positive electric charge.

The process for synthesis of such vinyl compounds is well known in the art, and the compounds are commercially available. They may be used alone or as a mixture. And they may be used together with a water-soluble, polymerizable and non-ionizable vinyl compound, such as acrylamide, N-hydroxy-methylacrylamide, methacrylamide, methyl methacrylate, vinylpyrrolidone, N,N-methylenebisacrylamide, triethyleneglycol dimethacrylate., polyethyleneglycol dimethacrylate.

When the non-ionizable vinyl compound is used together with the ionizable vinyl compound, the ratio of the amounts of the vinyl compounds must be carefully controlled according to their reactivity so as to make it sure that a substantial amount of the ionizable compound is incorporated in the polymer formed.

As a dye capable of having an electric charge when ionized, an ordinary acid dye or a basic dye can be used.

In case where a vinyl compound capable of forming polymer having a negative electric charge is used, a basic dye which has a positive electric charge should be used, and in case where a vinyl compound capable of forming polymer having a positive electric charge is used, an acid dye which has a negative electric charge should be used.

Also when gelatine is used as a binder for photographic emulsion, which is amphoteric electrolyte, dyeing must be conducted in due consideration of the isoelectric point of the gelatin. Thus, gelatin has a negative electric charge at pH higher than the isoelectric point of the gelatin, and has a positive electric charge at pH lower than the isoelectric point of the gelatin. Accordingly, in case where polymer having a negative electric charge is produced, the polymer images can be dyed without dyeing the gelatin by dyeing the images with a basic dye at a pH lower than the isoelectric point of the gelatin. It is also possible to dye the emulsion layer uniformly at first and then to wash it with a solution having lower pH value than the isoelectric point of the gelatin in order to remove dyestutf in the portions where no polymer image is formed, leaving dyed polymer image. Similarly, in case where polymer images having a positive electric charge are dyed with an acid dye, the polymer images can be dyed at a pH higher than an isoelectric point of the gelatin.

Although the most suitable pH value for dyeing changes with the kind of vinyl compound, dye or binder to be used, the most preferable range of pH value is 2.5 to 4.5 in case of a basic dye and, 5.0 to 8.0 in case of an acid dye when a gelatin treated with lime having an isoelectric point of about 4.9 is used as a binder.

Examples of dyes to be used in the present invention are, as acid dyes, C.I. Acid Yellow 7 (C.I. 56205), C.I. Acid Yellow 23, (C.I. 19140), C.I. Acid Red 1 (C.I. 18050), C.I. Acid Red 52 (C.I. 45100), C.I. Acid Blue 9 (C.I. 42090), C.I. Acid Blue 45 and C.I. Acid Violet 7 (C.I. 18055), and as basic dyes, C.I. Basic Yellow 1 (C.I. 49005), C.I. Basic Yellow 2 (C.I. 41000), (C.I. Basic Red 1, (C.I. 45160), C.I. Basic Red 2 (C.I. 50240), C.I. Basic Blue 25 (C.I. 52025), C.I. Basic Violet 3 (C.I. 42555) and C.I. Basic Violet 10 (C.I. 45170). Dye number abovementioned are due to Color Index (second edition).

These dyes have been sold with various commercial names.

In the present invention there may be used any of the electromagnetic waves and particle rays to which the ordinary photographic emulsions are sensitive. Thus, visible rays, ultraviolet rays, infrared rays of wave lengths not exceeding 1.3 micron, X-rays and 'y-rays and electron beams, a-rays and like particle rays can be used.

In carrying out the present invention, it is necessary to conduct the step of irradiation by electromagnetic Waves or particle rays, the step of reduction and polymerization, and the step of dyeing.

On irradiation by electromagnetic waves or particle rays, the silver halide grains may be dispersed in an aqueous solution or held in a dry gel. Thus, a highly viscuous or gelled photographic emulsion on a suitable support or substrate may be subjected to the irradiation, either in an undried state or in a dried state. As the reduction and polymerization take place concurrently, the reduction should be conducted in the presence of a vinyl compound or compounds. In the present invention, while both the vinyl compound and the compound as a reducing agent may be incorporated in the photographic emulsion before exposure, only one of them may be incorporated in the emulsion before exposure, the other being added to the system after the exposure and it is also possible to add both compounds after exposure.

As the reduction and polymerization must be conducted in the presence of water, it is necessary to conduct the reduction and polymerization in an aqueous solution or in a wet gel.

In general the reaction is conducted in the presence of a suitable quantity of an alkali, as it proceeds smoothly under alkaline conditions. While the amount of alkali suitable for the reaction depends on the kind of silver halide, of reducing agent and of high polymer in the system and their concentration and the reaction temperature, it is preferable to use an amount sufiicient to make the pH of the system 7.5 or more.

Furthermore, we have found that the polymerization of the vinyl compound in the process of the present invention is accelerated by the presence of sulfite ions in the system.

Sulfite ion may be added to the reaction system either in the form of a compound, which has originally contained the sulfite ion in the molecule, such as, alkali metal sulfites or ammonium sulfite, or in the form of a compound which will give a sulfite ion as the result of hydrolysis, such as, pyrosulfites of alkali-metals and ammonium or the adducts of bisulfites with aldehydes, such as, formaldehyde or glyoxal. Although the appropriate amount of sulfite ion to be added depends upon the nature and amount of the reducing agent and the vinyl monomer being used, the pH of the system and other factors, more than 0.05, especially more than 0.2 mole per liter of the system is effective.

In the case where the photographic emulsion is used in the form of a coated film on a support, the reaction can be performed by immersing the thus produced photosensitive material in an alkaline aqueous solution, after it has been exposed to the electromagnetic waves or particle rays. In this case the vinyl compounds and/or the reducing agents can be conveniently dissolved in the aqueous alkaline solution.

Although stopping of the reaction is readily achieved by adjusting the pH of the system to, e.g., or less, it may also be attained by cooling, removing the reactants by washing, dissolving the silver halide by fixation or adding a polymerization inhibitor to the system.

In the case where the high polymer as the vehicle forthe silver halide grains and the monomeric vinyl compound are mixed and coated together to form a film, it is preferable to add a small amount of an inhibitor for thermal polymerization in order to prevent the spontaneous thermal polymerization of the vinyl monomer. For such a polymerization inhibitor any of the known thermal radical polymerization inhibitors, such as p-methoxyphenol, hydroquinones, 2,6-di-tert, butyl-p-cresol, a-naphthol and the like, can be utilized.

When the vinyl monomer is contained in the system from the first, it is incorporated in an amount by weight of from to 30, and preferably from A to 4 times the amount of the high polymer which is originally present in the system. The silver halide is conveniently used in an amount by weight of from to 2, and preferably A to /2 times the amount of the high polymer which is originally present in the system. When the reducing agent is to be added to the system before the reaction, it is suitable to add it in the amount of from 1 to 20 moles per mole of the silver halide. It is convenient to add the thermal polymerization inhibitor in an amount of from 10 to 2000 ppm. of the weight of the vinyl compound. In the case where the vinyl monomers are dissolved in the processing solution, it is usually preferable to dissolve them in as high a concentration as possible, hence the preferable concentration of the monomer is determined mainly by the solubility of the monomer in the solution. In a case where the reducing agents are dissolved in the processing solution, it is suitable to dissolve them in a concentration between and 5 moles per liter, and preferably between A and 1 mole per liter.

It is similar to the ordinary silver halide photographic process that there can be any interval of time between the exposure to electromagnetic waves or particle rays and the processing of polymerization. In some cases, according to the characteristics of the photographic emulsion or the condition and the length of the interval, the effect of the exposure may be diminished to some extent and in this case the decrease in effect can be cancelled by increasing the amount of the exposure.

Polymer images can be formed by washing away only the unpolymerized portion of the vinyl monomer after exposure, reduction and polymerization, because the polymer is less soluble than the monomer and can scarcely diffuse through the high polymer such as gelatin which is used as a binder for a silver halide photographic emulsion. By utilizing monomers having at least two vinyl groups in combination, insolubility and non-dilfusibility of polymer obtained can be increased. Dye images corresponding to the polymer images are obtained by dyeing, as aforementioned, after polymerization. The images which are made by this procedure can be utilized as clear dye images by fixing a silver halide to remove it and then dissolving out the silver image by applying an oxidizing agent and a solvent for silver salts.

In case where a reducing agent having a high efiiciency of initiating polymerization is used in the present invention, it is unnecessary to remove silver images by the oxidation, since enough polymerization reaction is occurred already in such a condition that a very small amount of reduced silver is produced.

Further, the dye images thus produced can be transferred onto other supports. In carrying out a transfer, a support to be transferred must be brought into intimate contact with a layer containing dye images produced as abovementioned, which is wetted with a solvent for the dye such as methanol, water or an aqueous solution of acid, base or salt. As the supports on which the dye image is to be transferred, an ordinary paper or a paper or a film coated with hydrophilic polymer of gelatin can be used. When the dye image is to be transferred to a support which is coated by gelatin, it is preferable to treat itwith a mordant such as aluminum salts beforehand in the same way as the usual dye-transfer process. When once an image composed of the ionizable polymer is -made, it is possible to make a number of copies by dyeing and transferring as abovementioned, since a few copies can be made with one dyeing and a polymer image can be dyed repeatedly.

EXAMPLE 1 A photographic film bearing a layer of a gelatino silver chloroiodobromide emulsion was, after exposure, treated with a solution containing both resorcinol and sodium methacrylate to effect images forming polymerization and then, the resulting image composed of polyacrylic acid was dyed with a basic dye. The film was such that had been prepared by applying a subbing coat to both sides of a polyethylene terephthalate film, applying an antihalation layer to one of the surfaces of the so undercoated film and applying to the other surface a silver halide photographic emulsion, which was prepared by adding a suitable amount of merocyanine dyes with the sensitization maximum of about 550 mm., for the sake of optical sensitization and 1.5 g. of muccochloric acid as a hardening agent and adding further suitable stabilizing and wetting agents to a gelatino silver chloroiodobromide emulsion containing, per mol of silver, about 0.7 mol of chlorine, about 0.3 mol of bromine about 0.001 mol of iodine and about 100 g. of gelatin, to make a coated film containing 50 mg. of silver per 100 cm. and further applying on said emulsion layer a gelatin protective layer of about 0.8,u. thickness and is suitable for making line and half-tone images for the graphic arts. A sample of the film was exposed to light of 100 lux for 2 seconds through a negative of a line image, and then immersed under a red safe-light, in a solution of the following formulation:

Sodium acrylate g 36 Resorcinol g 2.6 2 N sodium hydroxide cc 16 Water cc 4.4

After 8 minutes of immersion at 35 C., the exposed area became brown. The sample was then soaked for 30 seconds in a 1.5% aqueous solution of acetic acid, and then fixed with a fixing solution of the following formulation:

Sodium thiosulfate (anhydride) g 150 Potassium pyrosulfite g Water to make cc 1000 The sample was fixed and washed completely and then immersed in a 0.1% aqueous solution of red basic dye (Rhodamine 6 GCP, C.I. Basic Red 1) for 5 minutes at room temperature. After dyeing, the sample was washed with a 5% aqueous solution of acetic acid for five minutes to remove the dye from the portions of the sample where the brown image had not formed, leaving the image portion containing the red dye. Since the brown image consisted of silver, it was easily dissolved out by Farmars reducer. After the removal of the silver image a clear red image was obtained. It was also possible to obtain the similar red image by reversing the order of the dyeing and the removal of the silver image, i.e., removing the silver image at first then dyeing the apparently colorless sample thus obtained.

The sample bearing the dye image thus formed were pressed on an ordinary paper which had been wetted with methanol by rubbing with a sponge containing methanol, and when the sample was separated from the paper after 30 seconds, the red image was transferred onto the paper.

When the same procedure as above was repeated using a 0.1% aqueous solution of Crystal Violet (Cl. Base Violet 3), Auramine 0-100 (C.I. Basic Yellow 2) or Basic Blue G.O. (Cl. Basic Blue instead of Rhodamine 6 GOP, the transferred images of blue-violet yellow or blue color Were obtained respectively.

In case of transferring dye images, it was unnecessary to remove silver images. A satisfactory image could be transferred by transferring immediately after a wash with water following the development and polymerization and a rinse in the stop bath.

12 EXAMPLE 2 A sample of the film as employed in Example 1 was exposed as in Example 1 and treated with a solution of the following formulation:

Sodium methacrylate g Resorcinol g 4.95 Sodium sulfite g 3.0 2 N sodium hydroxide cc 22 Water to make cc 75 By treatment at 30 C. for 8 minutes, faint brown silver images and images of polymethacrylic acid were obtained.

When the same procedure as Example 1 was repeated using an acid dye such as, Rhodamine 6 GCP or Crystal Violet, dye images were obtained and could be transferred onto a paper using methanol as Example 1.

EXAMPLE 3 A sample of the film as employed in Example 1 was exposed as in Example 1 and treated with a solution of the following formulation:

Acrylamide g 9 Potassium p-vinylbenzene sulfonate g 68 Resorcinol g 4.95 2 N sodium hydroxide cc 38 Water to make cc A sample of the film as employed in Example 1 was exposed as in Example 1 and treated with a solution of the following formulation:

l-vinyl-2,B-dimethylimidazolium-p toluenesulfonate g 75 S-methylresorcinol g 5.6 Potassium pyrosulfite g 3.0 2 N sodium hydroxide g 19 Water to make cc 75 1-vinyl-2,3-dimethylimidazolium-p-toluenesulfonate was obtained by reacting 1-vinyl-2-methy1imidazole with methyl p-toluenesulfonate at room temperature and recrystallizing the reaction products with ethanol and ether and its melting point was 142.5 C.

By treatment at 30 C. for 30 minutes, faint brown silver images and polymer images of quaternary salt were produced.

After fixing and washing as in Example 1, the sample was immersed in a 0.1% aqueous solution of Solar Rhodamine B extra (C.I. Acid Red 52) for 5 minutes, which was an acid dye having red color, and then was immersed in Kolthoffs buffer solution of pH 5.0 for 3 minutes and washed. After this washing, the sample in which the image area was dyed in red was obtained. A clear red image was obtained by dissolving the silver image as in Example 1. And the dye images thus formed could be transferred on an ordinary paper which was wetted with methanol as in Example 1.

Further, clear red images having high density were obtained by bringing the dye images into contact with a baryta paper, for 1 minute, which had been coated with a gelatin layer of 10p. thickness, dipped in a solution of alum and dried.

The similar sample was dyed with a 0.1% solution of Suminol Leveling Sky Blue R extra conc. (C.I. Acid Blue 62), which was an acid dye having blue color instead of Solar Rhodamine B extra. Blue color images were obtained by washing the film with a 1% solution of sodium bicarbonate. These images could be transferred on an ordinary paper wetted wtih ethanol. The similar result was obtained by using water instead of ethanol. Yellow color images were obtained by dyeing the sample with Solar Pure Yellow 8 G (C.I. Acid Yellow 7) or Tartrazine (C.I. Acid Yellow 23) instead of Solar Rhodamine B extra, and washing with the buffer solution of pH 5.0. These yellow color images were transferred on a paper wetted with methanol or water by pressing the images 14 the densities of the silver images in No. l and No. 2 of the samples were low, clear red colored images were recognized without removing the silver images.

These dye images were transferred on an ordinary paper by the same procedure as in Example 1.

EXAMPLE 7 Sample of the film as employed in Example 1 was exposed as in Example 1 and treated with solutions of the following formulation:

10 t the P l E MPLE Methacrylic acid 75 g.

XA Reducing agent As indicated in Table H.

Sulfites Do. A sample of the film as employed in Example 1 was ex- Water 75 cc. pofied as 11; Exarlnple 1 and treated with a solution of the 1 N NaOH Amount Sumcient to adjust the o owing ormu ation. pH to Table H.

TABLE II 13-cl1methylammoethylmethacrylate --g-- 40 Acrylamide g Reducing agent Sulfite Resorcinol g 5.0 20 Amt Amt, Potassium pyrosulfite g 3.0 P 0' Compound (s)- p Water 012.. 85 10---- N,I I-dimethy1metha- 0.2 Sodium su1fite- 12 9.0

minophenol. 11-.-. 1-amino;8-naphthol4i- 10.8 do 12 10.2 After treatment, at 30 C. for 20 minutes, basic polymer 12 1 sinfom aerd 13 6 15 1 d images were obtanied with faint brown silver images. i i- 3 5 3 33 12 Blue color images were obtained by dyeing the polymer gg g n e e pyro- 3 11.5 images with a solution of Suminol Leveling Sky Blue R f Su 1 extra cone. as in Example 4 and washing with an aqueous g ;fi? gp t 11.4 solution of sodium bicarbonate. 15--.- 5-arnino-2-naphthol 3 11, 16.--. sotdlitim Zg-gIEixyfiaph- 3 11.5

8.6116 S11 OHIO EXAMPLE 6 acid.

17...- 4chlororesorclnol-......- 3 9.0 S 1 f h film 1 d E 1 1 19-.-- 4,%dichloro1resiorii1l0l-.-. 3 11.5

amp es 0 t e as emp oye 1nxamp e were exeescorey a o e---. a 11.5 posed as in Example 1 and treated with solution of the g g f ggg gggf 3 ollo formulations: 21---. o-Hydroxyethylresominola 11.5 f Wmg 22--.. 2,4,6-tr1hydroxyacetos 11.5

phenonet: 23 3,5;dih ydroxybenzamido 3 11.5 Methacrylic acid 58.9 cc. igi gfig igf 3 Sodium carbonate monohydride 43.0 g. 25-..- 2,4fi6-3rihydroxybenzaldea 11.5

8. Reducmg agents as mdlcated 26---- 4-tctylresorcinol a 11.5 in Table 1: 27-.-- m-Hyfiroxy-moctanoyl- 3 11.5

am 6. Water 28-.-- Maleicacid(m qno-ma 11.5 1 N sodium hydroxide Amount suflicient to 29 hlytdrdorxyarfihrtlxe). 1 3 u 5 m- 0X BI]. aad ust the pH to g Y P y 10.0. 30-... m-Hydroxy(p-toluene- 3 11,5

sulfonyDanilide. 31.... Resgtrlcinolmonobutyl- 3 11.6 e GI After treatment at 30 C. for time as indicated 1n Table 32"" .pbenzylresminol 3 1, the samples were fixed, washed and dyed with a 0.1% gig i 3 11.6 solution of Rhodamine 6 GOP by the same procedure as 111 Resominolmonobenzo. 3 9 0 ate Example 35--.- 3ethylamino4-cresolnu' a 11.5 Transmission density to green light 1n the exposed areas 2,4,fi-trg ydrl'gxytoluerl e g and the unexposed areas of the samples was measured 35:: tgyg g gg ggggggg 3 1135 before and after dyeing. The results are summarized m 30.-.. Morin a 11.5 Table 1.

TABLE 1 Density of Density of T t unexposed areas exposed areas rea 1n Reducmg agent tim Before After Before After No. Compound -(e) y e y z y e y e in 1 5.6 10 0.02 0.12 0.04 0.08 1 7.3 10 0. 0a 0.22 0.00 0. 55 m-AminophenoL- 4.9 15 0.13 0.19 0.17 0.83 Z-methyhresorcin 5.6 20 0.44 1.00 0.72 2.28 4-etl1yl-resoreinol. 6. 3 10 0. 14 0. 61 0. 68 1. 18 4(m-hydroxyanih 11. 0 20 0. 12 0. 24 0.87 1. 0a 2-nitro-resorcinol- 7. O 4 0. 15 0. 50 0. 29 1. 48 1,3maphthalenediol- 7. 2 4 0. 26 0. 92 0. 47 1. 2,7-naphthalenediol 7.2 30 0.14 0.35 0.26 1. 25

It is greater in the exposed areas than in the unexposed areas, that is, the images corresponding to the exposed areas were dyed selectively. It was also evident from the fact that clear red colored images were obtained by removing silver was ascertained that the increase in density by dyeing 70 After treatment at 30 C. for 'such a time as indicated in Table III, fixing, washing and dyeing were conducted.

Optical density of the films thus obtained was measured images from the samples with Farmers reducer. Since as in Example 6 and summarized in Table III.

TABLE III Density of Density of unexposed areas exposed areas Treating time Before After Before After (min.) dying dying dying dymg 0. 09 0. 26 0. 13 0. 95 3 0. 34 1. 06 1.32 3. 58 10 0. 08 0. 11 0. 59 2. 30 25 0. 07 0. 0.09 1. 86 4 0. 47 1. 34 2.02 3. 49 5 0. 2O 0. 50 1. 15 2. 34 0.08 0. 11 0. 57 1. 28 20 0. 08 0.28 0. 13 1.68 6 0. 10 O. 45 0. 70 2. 20 30 0. 08 0.22 0. 31 2. 11 6 O. 10 0. 31 0.68 1. 81 20 0. 07 0. 18 0. l4 1. 42 2O 0. 12 0. 28 0. 17 0. 93 20 0. 08 0. 08 0. 43 1. 05 30 0. 08 0. 36 0. 01 0. 98 30 0. 36 0. 38 0. 38 2. 76 30 0. 12 1. 10 0. 44 2. 57 60 0. 14 0.28 0. 18 0. 54 60 0. 07 0. 34 0. 07 0. 48 0. 13 0. 38 0. 15 0.96 20 0.28 0. 66 0.27 2. 10 50 0. 19 0. 42 0. 35 2. 06 3 0. 07 2. 00 0. 68 2. 93 10 0. 08 0.23 0. 13 1. 73 5O 0. 06 1. 53 0. 06 1. 95 20 0. 10 0. 31 0. 45 1. 56 20 0. 18 0. 73 0.20 1. 92 3 0. 07 0. 92 0. 57 1. 88 3 0. 17 0. 61 0. 66 l. 46 0. 22 1. 28 0. 64 2. 09

The similar result as in Example 6 was obtained.

EXAMPLE 8 The following films A and B were treated with sodium methacrylate and l-amino-8-naphthol-3,6-disulfonic acid to effect the polymerization of vinyl compounds.

Film A is one that is usually employed in preparation of a positive for photogravure in photoengraving processes and is prepared by applying to both sides of a cellulose triacetate base a subbing layer, applying to one surface of the so subbed base an 'anti-halation layer, applying to the other surface of the base moderate grain size gelatino-silver halide emulsion, containing about 0.015 mole of iodine and about 0.985 mole of bromine and about 255 g. of gelatin per mole of silver, to which about 0.5 g. per 100 g. of gelatin, of muccochloric acid, as hardening agent, and a suitable stabilizer and surface active agents were added, in an amount to provide a coating layer containing 60 mg. of silver per 100 square centimeter, and applying thereover a protective layer of gelatin of 1 micron thickness.

Film B is one that is usually employed in preparation of line images or continuous tone images with steep gradation in photoengraving process and prepared by, to the same base as the film A, applying a fine grain gelatinsilver halide emulsion containing about 0.012 mole of iodine and about 0.988 mole of bromine and 204 g. of gelatin per mole of silver, and sensitized with a rhodanate complex of monovalent gold and combined with about 0.7 per 100 g. of gelatin, of cuccochloric acid as a hardening agent, 0.3 g. per 1 mole of silver, of 6-methyl- 4-hydroxy 1,3,3a,7-tetrazaindene as a stabilizing agent and a suitable surface active agent, in an amount to provide a coating layer containing 60 mg. of silver per 100 sp. cm., and applying thereover a protective layer of gelatin of about 0.8 micron thickness.

Each sample of films A and B was exposed through a step wedge .to a light having 1000 lux of luminous intensity and 2880/K. of color temperature for /2 seconds and then treated with the following solution:

Sodium methacrylate g 60 1-amino-8-naphthol-3,6-disulfonic acid g 12 Potassium pyrosulfite g 2.4 Water cc 60 2 N NaOH cc 22 After treatment at 30 C., faint brown images were recognized. Each sample fixed and washed by the same procedure as in Example 1 was divided into two parts. One part was dyed with Rhodamine 6 GCP as in Example 1. Density of two parts were measured as in Example 6.

FIG. 1 is characteristic curves of the film A showing relations between exposures and densities for each step of the wedge.

FIG. 2 is the similar characteristic curves of the film B.

In each figure, curve 1 shows a density of silver images before dyeing, and curve 2 shows a total density of dye and silver images. It was recognized that the absorbed amount of the dyestuff increased with the amount of the exposure. :In particular, with the medium amount of the exposure, considerable amount of dye image was formed while the silver image was almost imperceptible indicating that the polymerization was induced by the reduction of a very minute quantity of silver. This indicates that the process of the present invention can be used in preparation of not only line images but also continuous tone images. The samples having dyed images were wetted with water and were brought into contact with the papers which were the same as that used in Example 4 and wetted with a 1% solution of sodium bicarbonate and pressed. After three minutes standing the papers and the samples were separated and clear dye images on the papers were obtained.

EXAMPLE 9 A following panchromatic film was treated with a solution as in Example 8. The film is one that is usually employed in preparation of color separation negatives for photoengraving process and prepared by applying to both sides of a polyethylene terephthalate subbing layers, applying to one surface of the so subbed base an antihalation layer, applying to the other surface of the base a moderate grain size gelatino-silver halide emulsion, which contained about 0.05 mol of iodine and 0.95 mol of bromine and about 180 g. of gelatin per mole of silver, and was sensitized with a rhodanate complex of monovalent gold, then spectrally sensitized with thiacar-bocyanine derivative having about 630 m of sensitizing maxi mum and oxacarbocyanine having about 550 m of sensitizing maximum and added with 6-methyl-4-hydroxy-1,3, 3a,7-tetrazaindene as a stabilizing agent, dimethylol urea as a hardening agent and a surface active agent, in an amount to provide a coating layer containing mg. of silver per sq. cm., and applying thereover a protective layer of gelatin. Three samples of this film were exposed to a light having 1000 lux of luminous intensity and 2880 K. of color temperature for /2 second through, step wedge, each of the samples being brough into contact with red-, green-, and blue-filter, for color separation, and were treated with the same solution as in Example 8 at 30 C. for 14 minutes. When fixing, washing and dyeing were conducted as in Example 8, it was recognized that an amount of dye in the exposed areas of the films increased proportionally as exposure increased.

In this case, relative ratio of sensitivity to red, green and blue light was similar to the case of development with usual developing agent such as monomethylparamino phenol sulfate or hydroquinone.

EXAMPLE 10 A gelatino silver chloride photographic emulsion having centers of fog which had been prepared in the similar manner as disclosed in British patent specification 667,206, said emulsion containing pinakryptol yellow as a desensitizing agent, suitable hardening agents and surface active agents, were applied to a polyethyleneterephthalate film bearing a subbing layer. The photographic film being so-called autopositive photographic film utilizing Hershel effect was exposed to light of 2 kw. xenon arc lamp at 17 a distance of 50 cm. passed through a yellow filter for 2 minutes through an original, and then immersed in a solution of the following formulation:

Sodium methacrylate 50 g. 1 amino 8 naphthaol- 3,6-disulfonic acid 13 g. Potassium pyrosulfite 1.3 g. NaCl 1.0 g. NaOH Amount sufficient to adjust the pH of the solution to 10.0.

Water to make 100 cc.

After immersion at 30 C. for 7 minutes, the film was fixed, washed and dyed with Rhodamine 6 GCP as in Example 1. Brown color silver images were formed in the unexposed areas and dyed selectively. The reason why the only unexposed areas were dyed was due to the fact that polymethacrylic acid was produced only in the exposed areas, which was evident from the fact that a thickness of the unexposed areas was about 2 microns thicker than that of the exposed areas.

By treating the film with Farmers reducer to remove the silver images, clear red colored positive images corresponding to original were obtained.

EXAMPLE 11 A film as employed in Example 1 was exposed to X- rays for 3 seconds and treated with the same solution as employed in Example 1, using a cobalt X-ray tube made by Philips Co., at 30 kv., 10 ma. The film was partially covered with a razor blade of 0.2 mm. thickness and located 1 cm. from the window of the tube. The film was treated with the same solution as in Example 1 at 35 C. for 8 minutes, fixed, washed and dyed with Rhodamine 6 GCP. Silver images were produced only in the exposed areas and the exposed areas were dyed selectively.

Thus, it was shown that the process of the present invention is applicable to the silver halide photographic emulsion which is exposed to a high energy radiation other than visible light.

EXAMPLE 12 A polymerization and a dyeing were conducted using a photographic emulsion containing no gelatin, which Was produced by reacting silver nitrate with alkali halide in a solution of polyvinylpyrrolidone to prepare silver halide, coagulating polyvinylpyrrolidone and silver halide with acetone, removing by-product by decantation, dispersing the coagulated compositions and then ripening, said emulsion containing chlorine and bromine in molar ratio of 7:3, 100 g. of polyvinylpyrrolidone, 300 g. of polyvinylalcohol and 24x10" mol of sodium thiosulfate, as a chemical sensitizing agent, per mol of silver.

The emulsion thus formed was applied in a dark room to an undercoated cellulose triacetate film to form a coating layer of about microns in thickness. After drying, the photographic film was exposed to 500 watts xenon lamp at a distance of 50 cm. for 10 seconds through a line image of original, and treated with a solution of the following formulation After treatment at 30 C. for minutes, faint brown silver images were recognized. The film was immersed in a 1% aqueous solution of acetic acid to stop the reaction and directly washed with running water. Then, the image 18 areas remained but the non-image areas were dissolved away with water.

The image areas could be dyed with basic dyes as in Example 1. And then clear dye images were obtained by removing silver images from the film. Further, the dye images could be transferred on papers which had been wetted with methanol, in the same way as Example 1.

When methacrylamide was used instead of sodium methacrylate in the above solution, a polymeric image was also obtained but it could not be dyed with basic dyes.

When the processing solution did not contain methylene-bis-acrylamide, even the image area was swollen and dissolved by washing. From these facts it is evident that polymer composed of both sodium methacrylate and methylene-bis-acrylamide is formed in the image area.

Example 13 A film was produced by preparing a fine grain gelatino silver chlorobromide emulsion which contained silver chlorobromide, corresponding to about 64 g. of elementary silver and containing chlorine and bromine in molar ratio of 7:3, about 35 g. of gelatin per liter of the emulsion, said fine grain gelatino silver chlorobromide photographic emulsion being pH 5.8 and pAg 7.7, adding to 35 cc. of said photographic emulsion a solution which contained cc. of 0.43 mol aqueous solution of methacrylic acid, 1 cc. of 1 wt. percent aqueous solution of sodium dodecylbenzene sulfonic acid, 1 cc. of l/50 mol aqueous solution of mucochloric acid, '1 cc. of l/ 50 mol aqueous solution of paramethoxyphenol and 6.5 g. of gelatin, and applying the gelatino silver chlorobromide photographic emulsion to an undercoated cellulose triacetate film base so that the thickness of the emulsion layer after drying becomes 8 microns.

The film thus formed was brought into intimate contact with a transparent original having line images, exposed to 500 watts Xenon lamp at a distance of 50 cm. for 1 second and coated with a solution of the following formulation:

The treating solution was immersed into a sponge-like synthetic resin and the film was coated therewith. A glass plate was placed on the film to cover the surface of the wet emulsion. After leaving the film at room temperature for 20 minutes, color of the exposed areas changed and faint silver images were recognized. By treatment as in Example 1, the exposed areas were dyed selectively.

It was possible as in Example 1 that clear dye images were obtained by removing silver images and were transferred on a paper by using methanol.

What is claimed is:

1. A process for forming dye images which comprises:

(a) subjecting a photographic silver halide emulsion layer, which has received selective exposure to radiation such that centers for developing have been created within a pattern of the silver halide grains, to contact with at least one compound selected from the group consisting of resorcinol, derivatives of resorcinol, m-aminophenol, derivatives of m-aminophenol, naphthol derivatives having two hydroxy groups on the naphthalene ring and naphthol derivatives having one hydroxy group and one amino group on the naphthalene ring, said two hydroxy groups or said one hydroxy group and said one amino group being at the l,6-position, the 1,8-position, the 2,5- position or the 2,7-position on the naphthalene ring, in the presence of a polymerizable vinyl monomer capable of being electrically charged by ionization or by addition of a hydrogen ion.

19 (b) polymerizing said vinyl compound, in the presence of water, with the developing centers of'the silver halide grains and simultaneously reducing said silver halide grains 'which contain centers for developing with the at least one compound selected from the said group to thereby produce a pattern of substantially colorless to light -brown ionizable vinyl polymer which is coexistent with said pattern of said silver halide grains which contain centers of development, and dyeing the resulting ionizable polymer with a dye having an electric charge opposite to the polymer, whereby there is obtained a polymer image pattern of a color attributable to, and in accordance with, said dye.

2. The process as claimed in claim 1 wherein said vinyl compound is selected from the group consisting of acrylate, methacrylate and p-vinylbenzene sulfonate and said dye is a basic dye.

3. The process as claimed in claim 1 wherein said vinyl compound is selected from the group consisting of l-vinyl- Z-methyl imidazole, its quaternary salts, S-dimethylaminoethylmethacrylate and its quaternary salts and said dye is an acid dye.

4. The process as claimed in claim 1 wherein said vinyl compound capable of being electrically charged is used together with a polymerizable vinyl compound or compounds which have no electric charge.

5. The process as claimed in claim 1 wherein said polymerization is carried out in the presence of sulfite ion.

6. The process of claim 1 wherein said compound is a derivative selected from the group consisting of:

resorcinol-monoacetic acid ester, resorcinol monoethylether, 2-methyl-resorcinol, S-methyl-resorcinol, 4-ethyl-resorcinol, 4-hexyl-resorcinol,

3,5-dihydroxy benzoic acid, 2,6-dihydroxy benzoic acid, 2-nitroresorcinol,

phloroglucinol, 1,3-naphthalene-diol,

m- (dimethylamino phenol, 4-hydroxy-N,N-dimethyl-o-toluidine, 3-(m-hydroxyanilino)-l-propane-sulfonic acid m-hydroxyphenylglycine, m-(benzylamino)phenol, m-(fl-hydroxyethylamino)phenol, m-(B-chloroethylamino)phenol, resorcinolmonoethylether, resorcinolmonobutylether, resorcinolmonobenzoate, o-hydroxyethylresorcinol, 4-n-propylresorcinol, 4-t-octylresorcinol, 4-n-laurylresorcinol, 4-cyclohexylresorcinol, 4-benzylresorcinol, 2,4,6-trihydroxybenzoic acid, 2,4,6-trihydroxytoluene, 2,4,G-trihydroxybenzaldehyde, 3,S-dihydroxy-4-methylbenzoic acid, 2,6-dihydroxybenzamide, 3,5-dihydroxybenzamide, 2,6-dihydroxy-4-methylbenzaldehyde, 2,6-dihydroxyacetophenone, 2,4-dihydroxypropiophenone, 2,4,6-trihydroxyacetophenone, 2,2,4,4-tetrahydroxybenzophenone, phlorizine,

fi-resorcilaldoxime 4-chlororesorcinol, 4,6-dichlororesorcino1,

20 2,4-dihydroxybenzene sulfonic acid, m-hydroxy-n-octanoylanilide,

m- (propionylamino) phenol,

m-(propenylamino) phenol,

maleic acid mono(m-hydroxyanilide),

succinic acid mono (m-hydroxyanilide),

m- (acetoacetylamino )phenol,

m-benzoylaminophenol,

phthalic acid mono(m-hydroxyanilide),

m-hydroxy(p-toluenesulfonyl),

5,7-dihydroxy-4-hydroxyflavone,

5,7-dihydroxy-4'-methoxyfiavone,

morin,

3-ethylamino-4-cresol,

m-propylaminophenol,

m-octylaminophenol,

m-n-decylaminophenol,

4- (m-hydroxyanilino l-butane,

m-diethylamino phenol,

m-hydroxydiphenyl amine,

1,6-dihydroxynaphthalene,

1,S-dihydroxynaphthalene,

2,7-dihydroxynaphthalene,

1,8-dihydroxynaphthalene-2,4-disulfonic acid,

1,8-dihydroxynaphthalene-3,5-disulfonic acid,

1,8-dihydroxynaphthalene-3,6-disulfonic acid,

2,7-dihydroxynaphthalene-3,6-disulfonic acid,

1-amino-6-naphthol,

3-(6-hydroxy-l-naphthylamino)propane-1- sulfonic acid,

1-amino-8-naphthol,

N-acetyl-1-amino-8-naphthol,

Z-amint'rS-naphthol,

2-amino-7-naphthol,

1-amino-8-naphthol-2,4-disulfonic acid,

2,7-dioxynaphthalene monomethyl ether,

1-amino-8-naphthol-3,S-disulfonic acid,

1-amino-8-naphthol-3,6-disulfonic acid,

1-amino-8-naphthol-4,6-disulfonic acid,

1-amino-8-naphthol-5,7-disulfonic acid,

l-amino-8-naphthol-4-su1fonic acid,

S-amino-1-naphthol-4-sulfonic acid,

2-amino-5-naphthol-7-sulfonic acid.

7. The process of claim 1 wherein said compound is said resorcinol derivative.

8. The process of claim 1 wherein said compound is said m-amino phenol derivative.

9. The process of claim 1 wherein said compound is said naphthol derivative.

10. The process of claim 1 wherein dyeing is with a basic dye and is conducted at a pH of 2.5 to 4.5.

11. The process of claim 1 wherein dyeing is with an acid dye and is conducted at a pH of 5.0 to 8.0.

12. The process of claim 1 wherein polymerization is conducted under alkaline conditions at a pH of 7.5 or greater.

13. The process of claim 1 wherein said vinyl monomer 1s present in combination with a polymeric vehicle for said silver halide grain.

14. :Ihe process of claim 13 wherein said vinyl monomer 1s present, prior to exposure, in an amount of 3 to 30 times, by weight, of the amount of polymeric vehicle, in combination with from ,5 to 2 times by weight of the polymeric vehicle of silver halide.

15. The process of claim 14 wherein said at least one compound is present prior to exposure in an amount of said at least one compound from to 20 moles per mole of silver halide.

16. The process of claim 1 wherein said emulsion layer is subjected to said at least one compound by contacting said emulsion layer with said at least one compound in a concentration of to 5 moles per liter of processing solution.

17. The process of claim 1 wherein portions of the emulsion which do not contain centers of development 21 and which accordingly are not polymerized are removed subsequent to polymerization.

18. The process of claim 1 wherein said reduced silver halide grains are, subsequent to polymerization, removed from said vinyl polymer pattern, whereby the color of said dyed pattern is substantially solely due to the coloring action of said dye.

19. The process of claim 9 where said naphthalene ring is substituted with said two hydroxy groups or said one hydroxy group and said one amino group at the 1,6- positions.

20. The process of claim 9 where said naphthalene ring is substituted with said two hydroxy groups or said one hydroxy group and said one amino group at the 1,8- positions.

21. The process of claim 9 where said naphthalene ring is substituted with said two hydroxy groups or said one hydroxy group and said one amino group at the 2,5- positions.

22. The process of claim 9 where said naphthalene ring is substituted with said two hydroxy groups or said one hydroxy group and said one amino group at the 2,7- 11051110115.

23. The process of claim 1 wherein said compound is resorcinol.

24. The process of claim 1 wherein said compound is m-aminophenol.

25. The process of claim 7 where said polymerization is carried out in the presence of sulfite ions.

26. The process of claim 8 where said polymerization is carried out in the presence of sulfite ions.

27. The process of claim 9 where said polymerization is carried out in the presence of sulfite ions.

28. The process of claim 23 where said polymerization is carried out in the presence of sulfite ions.

29. The process of claim 24 where said polymerization is carried out in the presence of sulfite ions.

30. The process of claim 1 wherein said naphthalene ring is substituted with said two hydroxy groups.

31. The process of claim 1 wherein said naphthalene ring is substituted with said one hydroxy group and said one amino group.

References Cited UNITED STATES PATENTS 2,887,376 5/1959 Tupis 9635.1 3,019,104 1/196'2 Oster 96-29 OTHER REFERENCES C. E. K. Mees, The Theory of the Photographic Process, Third Edition (1967), p. 289 (cited by applicants in parent).

C. E. K. Mees, The Theory of the Photographic Process, 1947, pp. 356-357.

RONALD H. SMITH, Primary Examiner US. Cl. X.R. 96-35.1, P 

